The average orientation and flexibility of the phosphorylcholine group are deduced from deuterium and phosphorus-31 nuclear magnetic resonance measurements of unsonicated phosphatidylcholine bilayers in the liquid crystalline state. The experimental data are consistent with a model in which the polar head group exhibits a restricted flexibility characterized by rapid transitions between two enantiomeric conformations. A completely flexible or a completely rigid head group structure can be excluded. The phosphorylcholine residue is found to be bent at the position of the phosphate group, due to a gauche-gauche conformation of the phosphodiester linkage. The choline dipole is aligned parallel to the plane of the membrane, which is in agreement with X-ray and neutron diffraction studies. The average orientation of the phosphorylcholine group is therfore the same as that of the phosphorylethanolamine head group.